Proofreading experimentally assigned stereochemistry through Q2MM predictions in Pd-catalyzed allylic aminations

Autor segons l'article: Wahlers, Jessica; Margalef, Jessica; Hansen, Eric; Bayesteh, Armita; Helquist, Paul; Dieguez, Montserrat; Pamies, Oscar; Wiest, Olaf; Norrby, Per-Ola

Departament: Química Física i Inorgànica

Autor/s de la URV: Diéguez Fernández, Montserrat / Margalef Pallarès, Jèssica / Pamies Ollé, Oscar

Paraules clau: Stereochemistry; Prediction; Palladium; Molecular mechanics; Molecular analysis; Mechanics; Ligand; Follow up; Experimental study; Enantiomer; Drug synthesis; Conformational transition; Chemistry; Catalysis; Article; Amination

Resum: The palladium-catalyzed enantioselective allylic substitution by carbon or nitrogen nucleophiles is a key transformation that is particularly useful for the synthesis of bioactive compounds. Unfortunately, the selection of a suitable ligand/substrate combination often requires significant screening effort. Here, we show that a transition state force field (TSFF) derived by the quantum-guided molecular mechanics (Q2MM) method can be used to rapidly screen ligand/substrate combinations. Testing of this method on 77 literature reactions revealed several cases where the computationally predicted major enantiomer differed from the one reported. Interestingly, experimental follow-up led to a reassignment of the experimentally observed configuration. This result demonstrates the power of mechanistically based methods to predict and, where necessary, correct the stereochemical outcome. © 2021, The Author(s).

Àrees temàtiques: Zootecnia / recursos pesqueiros; Saúde coletiva; Química; Psicología; Planejamento urbano e regional / demografia; Physics and astronomy (miscellaneous); Physics and astronomy (all); Odontología; Nutrição; Multidisciplinary sciences; Multidisciplinary; Medicina veterinaria; Medicina iii; Medicina ii; Medicina i; Materiais; Matemática / probabilidade e estatística; Interdisciplinar; Geociências; General physics and astronomy; General medicine; General chemistry; General biochemistry,genetics and molecular biology; Farmacia; Engenharias iv; Educação física; Ciências biológicas iii; Ciências biológicas ii; Ciências biológicas i; Ciências ambientais; Ciências agrárias i; Ciência da computação; Chemistry (miscellaneous); Chemistry (all); Biotecnología; Biodiversidade; Biochemistry, genetics and molecular biology (miscellaneous); Biochemistry, genetics and molecular biology (all); Astronomia / física; Antropologia / arqueologia

Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/

Adreça de correu electrònic de l'autor: oscar.pamies@urv.cat; montserrat.dieguez@urv.cat

Data d'alta del registre: 2025-02-24

Versió de l'article dipositat: info:eu-repo/semantics/publishedVersion

Enllaç font original: https://www.nature.com/articles/s41467-021-27065-2

URL Document de llicència: https://repositori.urv.cat/ca/proteccio-de-dades/

Referència a l'article segons font original: Nature Communications. 12 (1): 6719-

Referència de l'ítem segons les normes APA: Wahlers, Jessica; Margalef, Jessica; Hansen, Eric; Bayesteh, Armita; Helquist, Paul; Dieguez, Montserrat; Pamies, Oscar; Wiest, Olaf; Norrby, Per-Ola (2021). Proofreading experimentally assigned stereochemistry through Q2MM predictions in Pd-catalyzed allylic aminations. Nature Communications, 12(1), 6719-. DOI: 10.1038/s41467-021-27065-2

DOI de l'article: 10.1038/s41467-021-27065-2

Entitat: Universitat Rovira i Virgili

Any de publicació de la revista: 2021

Tipus de publicació: Journal Publications